Process of making ether compounds



Patented Oct. 24, 1944 raocuss OF MAKING ETHER COMPOUNDS Max Engelmann,Wilmington, Del., an Josef Pikl, Glassboro, N. J.

,' assignors to E. I. du Pont de Nemours & Company, Wilmington, DeL, acorporation of Delaware No Drawing. Application December 30, 1941,

Serial No. 424,904

2 Claims. (Cl. 260-404) I This application is a continuation-in-part ofour co-pending application Serial No. 356,356. filed September 11, 19.40(and issued March 16, 1942 as Patent No. 2,313,741), and relates tonovel organic compounds which may be designated generally as ethers oforganic amido methylol compounds.

It is an object of this invention to produce novel organic derivativesof amido-methylol compounds by etherifying the OH group of the methylolradical. It is a further object of this invention to produce novelorganic compounds having valuable surface-active properties. Other andfurther important objects of this invention will appear as thedescription proceeds.

We have found that methylol-amides react readily with compoundscontaining alcoholic hyolroxyl groups according to the following,reaction:

in this equation R is an aliphatic, aromatic,.

araliphatic, or cycle-aliphatic radical, which may be attached to the COgroup directly or through the agency of a non-carbonic link such as O, Sor NH, and preferably contains no water-solubilizing groups, while R."is.hydrogen or an organic radical. As hydroxy compounds, to react asabove with the methylol amides, one may use aliphatic or aromaticalcohols, polyhydroxy compounds, hydroxy-carboxylic acids,hydroxy-phosphonic acids, a hydroxy-alkyl-sulfonic acid or their esters,amides and other derivatives which still contain the- OH group.

This application is concerned primarily with those compounds wherein Ris free from watersolubilizing groups.

As a special subgroup of our generic invention above come the others ofthe general formula v R-CONH-CH2OR' wherein R is an aliphatic orcycloaliphatic radical containing at least '7 carbon atoms and attachedto the CO group directly or through the agency of oxygen, sulfur or anitrogen atom. If in this formula R is selected so as to havewatersolubl groups, such as the carboxy, sulfonic or phosphonic acidradical, the resulting ether compounds form valuable agents for aqueoustreatmethylol compounds and of hydroxyl-bearing compounds are mentionedat this point, without any intent, however, to limit our invention tothese instances.

I A. Typical mcthyZoZ compounds Methylol-stearamide CmH3e-CONH-'-CH20H wMethylol amide of naphthenic acid.

Methylol amide of hydroabietic acid. Dimethylol of distearamido-methane:

B. Typical hydrorryl-beafing' cmnprmnds (etherifying agents) 8 Methanol:

' HO-CH: Ethanol. Isopropyl alcohol. Octyl alcohol. Cyclohexanol.

Ethylene glycol:

HOCH2CH2OH Benzyl alcohol noomcsm Glycollic acid:

.HO-C"H2COOH Glycollic-acid ethyl-ester:

HO-OI-Iz-CO-OCzHs It will be clear that by various combinations of thecomponents in the two tables, numerous and varied ethers may beobtained.

The reaction between the methylol amides and the hydroxyl-group bearingcompounds may be carried out by reacting the components, preferably inthe presence of a catalyst. For the latter purpose, a small amount of ananhydrous, acid reacting condensing agent may be used, such as PCla,POC13, maleic anhydride, concentrated sulfuric acid, or anhydrouhydrogen chloride. If desired an inert diluent such as acetone, ethyl 60acetate or dioxane, may be used in carrying out this condensation. The.reaction temperature may vary from about to about 100 C. The reactionmay be carried out by reacting one mol of the methylol amide with onemol of the hy-' droxy compound, but generally an excess of the hydroxycompound will be desirable in orderto carry the reaction to completionas far as possible. In many cases the hydroxy compound may be used insuch a quantity as to serve also as a solvent or diluent for thereaction. In'many cases, the methylol compound may be replaced by thecorresponding methylene halide,.for instanceStearamido-methylene-chloride:

CirHss-CONH-CHaCl Bis-chloromethyl-distearamido -methane etc.

The group of products which are obtained with hydroxy compoundscontaining free acid groups are soluble in dilute alkaline aqueousmedia. Those free from water-solubilizing groups are soluble in organicmedia such as acetone, carbon tetrachloride, benzene, solvent naphtha,pyridine, etc. Both types are quite stable in neutral or basic media andmay even be heated for a considerabie length of time. They are, however,very sensitive to acids. If the sodium salt, for instance, ofstearamido-methoxy-glycollic acid, CnHzsCO-NHCH:OCH2COOH, is acidifiedwith hydrochloric acid, the free glycollic acid is first precipitatedwhich can be brought back into solution by addition of a base. ever, theacidified solution is heated for a few minutes, an insoluble product isformed which cannot be dissolved again by the addition of acharacterized by surface-active properties, as a result of which theymay be used variously in the textile-treatment arts, for instance assoftening agents, or as dye-fixing, starch-fixing or waterproofingagents. For the latter purpose, the compounds having a long alkyl chain,say over '7 carbon atoms, are of special interest. The water-repellenteffect on textile fiber obtained by the aid of these compounds is of apermanent nature, in the sense that it is not destroyed by repeatedwashings with soap or by dry-cleaning agents.

In order to obtain this eifect, the textile material is impregnated witha 1 to 2% solution of the amido-ether in an organic solvent, forinstance acetone or benzene, or with an aqueous emulsion of equivalentstrength, preferably in the presence of an organic-soluble orwater-soluble (respectively) acid reagent, such as oxalic or aceticacid, and then subjected to a heat treatment for a few minutes at 100'to170 C. It is' believed that the decomposition products obtained by acidhydrolysis as described above are the active principles for theproduction of the permanent water repellent and softening effect. It istherefore desirable to add to the treatment bath a carboxylic acid, asabove indicated, or any other reagent which will produce a temporaryacid reaction during the baking step. Such other addition products whichhave been found to be effective are, for instance, ammonium chloride,pyridine hydrochloride, ammonium thic- II, howcyanate or-a combinationof thiourea or urea and ammonium chloride.

The novel products may also be used in combination with otherwaterproofing agents such as wax-emulsions. or in combination with othertypes of permanent water-repellency agents, for instance thequaternary-ammonium compounds described in U. S. Patent No. 2,146,392,or the amidomethvl-phosphonic acids of our copending application SerialNo. 322,766 (Patent No. 2,304,- 156, issued December '8, 1942), or thevarious water-repellency agents of the isocyanate and ketene classes,provided these other agents mentioned are judiciously selected so as tobe compatible with the particular solvent (or aqueous emulsion) employedfor the treatment bath.

The new products present great advantages over other products used forimparting permanet water-repellency, for instance the quaternarypyridinium compounds oi. U. S. Patent No. 2,146,- 392, above referredto. First of all, no pyridine is needed for the preparation of our novelproducts, and the use of these products thus eleminates a great safetyhazard and health hazard in the application. Another advantage is themuch greater stability of the products which facilitates greatly theapplication of the prods ucts, eliminating especially the lowtemperature drying step imperative in the aforegoing pyridiniumcompounds.

Without limiting our invention to any particular procedure, thefollowing examples are given to illustrate our preferred mode ofoperation. Parts mentioned are by weight.

Example 1 a melting point of 88 to 89 C. It is soluble in ethyl alcohol,benzene, ether, carbon-tetra-chloride, but insoluble in water.

Nitrogen analysis: Found, N=4.50%. Calculated for C17Ha5CO.NH.CH2OCHs,N=4.28%.

This product was applied to cotton fabric from an acetone solution at astrength of 1% in the presence of 1% of oxalic acid and then subjectedto a baking treatment for 10 minutes at 150 C. It gave a stronglywater-repellent finish which was only slightly removed by washing.

Example 2 parts of benzyl alcohol and 15 parts of stearamido-methanolwere thoroughly mixed, and a mixture of 0.5 part ofphosphorus-oxychloride, diluted with 10 parts of benzyl alcohol, wereadded. The reaction mass was heated while stirring for 2 hours at atemperature of 60 Q. After about one-half hour the mixture became clear.After cooling down to room temperature, the reaction product wasfiltered and recrystallized from methyl alcohol. It was found to melt at86.5 to 87 C. It is soluble in alcohol, ether, benzene, acetone andcarbon tetrachloride but insoluble in water. When heated with 50%sulfuric acid it gives the characteristic odor of benzyl alcohol. N -analysis=3.53%. The

Example 3 To 100 parts of octyl alcohol there were added To 100 parts ofoctyl alcohol there were added 20 parts of methylol benzamide, and themixture was then warmed to 40 to 45 0., while a slow stream of hydrogenchloride was being passed into the reaction mixture. After 30 minutes,400 parts of ether were added to the reaction mass and the latter wasthen cooled with a freezing mixture to 30 C. The reaction productcrystallized readily at this temperature and was filtered rapidly. Itmelted sharply at 48 C., and was recrystallized from a mixture ofalcohol and water.

The analysis indicated that it was most prob ably the expected octylether of methylol benzamide, of the formula hydroxymompounds, exceptcellulose, provided care is taken that the hydrogen halide which isformed in the reaction does not decompose the product.

This may be accomplished by reducing the reaction time to the shortestpossible limit and by discouraging activity on the part of the hydrogenhalide either by cooling down the reac- It will be understood that manyvariations in the details of procedure may be practiced, with-- outdeparting from the spirit of this invention.

As methylol amides one may use any of the fatty-acid methylol-amides,which may he saturated or unsaturated, straight-chain, branched chain orcyclo aliphatic, and also the methylol compounds of the correspondingalkyl or acyl ureas or carbamates, such as octadecyl-carbamate. One mayalso use methylol amides of aromatic or araliphatic acids, for instancethe amides of naphthenic acid or hydro-abietic acid. The methylolcompounds may be substituted by various substituents, exceptwater-solubilizing groups, and may be derived from monoor polycarboxylicacid amides. Other methylol compounds useful for this reaction may beprepared by decomposing chloromethylamides such as are disclosed in U.S. P. 2,131,362 or in copending application of M. A. T. Rogers, SerialNo. 286,944 (or corresponding British Patent No. 517,474), by treatmentwith water or basic compounds, for instance potassium carbonate.

Furthermore, as already mentioned above, the use of methylol-amides maybe dispensed with by substituting in their place the correspondingmethylene-halides. Thus, chloromethyl stearamide ormethylene-di(stearamidomethyl chloride) may be reacted with any of theaforegoing hydroxyl-bearing compounds, for instance methyl, octyl orbenzyl alcohol or other monoorpolytion mass promptly after completion ofthe reaction, or by neutralizing the hydrogen halide formed in thereaction, or by diluting the latter to a pointwhere its activity is veryweak.

Still another way for the preparation of the novel compounds of thisinvention is the simultaneous reaction of a higher fatty-acid amide withformaldehyde and the selected hydroxycompound at about 50 C., in thepresence of an acid catalyst as above defined.

As for the methylol-amides employed as initial materials for thisinvention, these may be prepared by standard methods; for instance, 'byheating (to about 50 or C.) the corresponding carhoxylic acid amide withparaformaldehyde, or other source of formaldehyde, in an inorganicliquid medium, such as methyl or ethyl alcohol, benzene, toluene orpyridine, in the presence of an acid absorbing agent, for instancepotassium carbonate, sodium carbonate or pyridine. See for instance, U.S. Patents Nos. 2,146,392 and 2,212,654.

The methylene halides employed as an alternative ior our initialmaterials as above indicated, are generally prepared by reacting withparaformaldehyde on the corresponding carboxylic acid amides in thepresence of dry hydrogen chloride. See for instance, U. S. Pat. No.2,131,362, British Patent No. 492,699 and copending application ofRogers, Serial No. 286,944 (or corresponding British Patent No.517,474).

We claim:

1. The process of producing novel organic compounds which comprisesreacting with a hydroxyl-bearing compound of the general formula HO-R,wherein R stands for a hydrocarbon radical selected from the groupconsisting of alkyl, cycloalkyl and aralkyl, upon an amido-methylenecompound of the general formula n-c O-NCH2X wherein R is an organicradical free from watersolubilizing groups; R" is a member of the groupconsisting of hydrogen and organic radicals free from water-solubilizinggroups, while X stands for a member of the group consisting of halogenand the hydroxyl group, and recovering the resulting ether compound.

2. The process of producing novel ether compounds which comprisesreacting upon a compound of the general formula z-comi-cm-x wherein Z isan aliphatic radical free from watersolubilizing groups and containingat least 7 carbon atoms and X stands for a member of the groupconsisting of halogen and hydroxy, with a hydroxyl-bearing compound ofthe general formula HO-R', wherein R' stands for a hydrocarbon radicalselected from the group consisting of alkyl, cycloalkyl and aralkyl.

MAX ENGEIMANN. JOSEF PIKL.

